JP5970000B2 - An azeotrope-like composition of trans-1,1,1,4,4,4-hexafluoro-2-butene and water - Google Patents
An azeotrope-like composition of trans-1,1,1,4,4,4-hexafluoro-2-butene and water Download PDFInfo
- Publication number
- JP5970000B2 JP5970000B2 JP2013550529A JP2013550529A JP5970000B2 JP 5970000 B2 JP5970000 B2 JP 5970000B2 JP 2013550529 A JP2013550529 A JP 2013550529A JP 2013550529 A JP2013550529 A JP 2013550529A JP 5970000 B2 JP5970000 B2 JP 5970000B2
- Authority
- JP
- Japan
- Prior art keywords
- hfo
- azeotrope
- composition
- 1336mzz
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000203 mixture Substances 0.000 title claims description 84
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 38
- NLOLSXYRJFEOTA-OWOJBTEDSA-N (e)-1,1,1,4,4,4-hexafluorobut-2-ene Chemical group FC(F)(F)\C=C\C(F)(F)F NLOLSXYRJFEOTA-OWOJBTEDSA-N 0.000 title claims description 5
- 238000009835 boiling Methods 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 13
- 239000007788 liquid Substances 0.000 description 12
- 239000012535 impurity Substances 0.000 description 10
- OHMHBGPWCHTMQE-UHFFFAOYSA-N 2,2-dichloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)C(Cl)Cl OHMHBGPWCHTMQE-UHFFFAOYSA-N 0.000 description 5
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 239000004604 Blowing Agent Substances 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000008282 halocarbons Chemical class 0.000 description 3
- 239000003507 refrigerant Substances 0.000 description 3
- 230000001954 sterilising effect Effects 0.000 description 3
- 238000004659 sterilization and disinfection Methods 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 239000003380 propellant Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- LDTMPQQAWUMPKS-OWOJBTEDSA-N (e)-1-chloro-3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)\C=C\Cl LDTMPQQAWUMPKS-OWOJBTEDSA-N 0.000 description 1
- NLOLSXYRJFEOTA-UPHRSURJSA-N (z)-1,1,1,4,4,4-hexafluorobut-2-ene Chemical compound FC(F)(F)\C=C/C(F)(F)F NLOLSXYRJFEOTA-UPHRSURJSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 239000004338 Dichlorodifluoromethane Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000779 depleting effect Effects 0.000 description 1
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 1
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000005437 stratosphere Substances 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- 229940029284 trichlorofluoromethane Drugs 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C21/00—Acyclic unsaturated compounds containing halogen atoms
- C07C21/02—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds
- C07C21/18—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
- C07C17/383—Separation; Purification; Stabilisation; Use of additives by distillation
- C07C17/386—Separation; Purification; Stabilisation; Use of additives by distillation with auxiliary compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/143—Halogen containing compounds
- C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
- C08J9/146—Halogen containing compounds containing carbon, halogen and hydrogen only only fluorine as halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/30—Materials not provided for elsewhere for aerosols
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
- C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
- C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
- C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/09—Geometrical isomers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/10—Water or water-releasing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/16—Unsaturated hydrocarbons
- C08J2203/162—Halogenated unsaturated hydrocarbons, e.g. H2C=CF2
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/18—Binary blends of expanding agents
- C08J2203/182—Binary blends of expanding agents of physical blowing agents, e.g. acetone and butane
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/10—Components
- C09K2205/12—Hydrocarbons
- C09K2205/126—Unsaturated fluorinated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/32—The mixture being azeotropic
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Dispersion Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Detergent Compositions (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Description
本発明は、トランス−１，１，１，４，４，４−ヘキサフルオロ−２−ブテン（１３３６ｍｚｚｍ又はＨＦＯ−１３３６ｍｚｚ（Ｅ））及び水の共沸性及び共沸混合物様の組成物に関する。 The present invention relates to trans-1,1,1,4,4,4-hexafluoro-2-butene (1336mzzm or HFO-1336mzz (E)) and water azeotrope and azeotrope-like compositions.
トリクロロフルオロメタン及びジクロロジフルオロメタンのようなクロロフルオロカーボン（ＣＦＣ）は、伝統的に冷媒、発泡剤、及びガス滅菌用の希釈剤として用いられている。近年においては、全ハロゲン化クロロフルオロカーボンは地球のオゾン層に対して有害である可能性があるという一般的な懸念が存在する。したがって、成層圏により安全なこれらの材料に対する代替物が望まれている。現在は、塩素置換基をより少ししか含まないか又は全く含まないフッ素置換炭化水素を用いる世界的な努力が存在する。ＨＦＣ、即ち炭素、水素、及びフッ素のみを含む化合物の製造は、ＣＦＣに対する代替物を与える環境的に望ましい製品を与えるための興味深い主題である。フッ化水素を種々のヒドロクロロカーボン化合物と反応させることによってかかる化合物を製造することが、当該技術において公知である。ＨＦＣは、非オゾン層破壊性ではないので、ヒドロクロロフルオロカーボン（ＨＣＦＣ）又はクロロフルオロカーボン（ＣＦＣ）よりも遙かにより環境的に有利であると考えられているが、最近のデータは、これらはまた温室効果地球温暖化の一因となる可能性があることを示している。したがって、ＨＦＣ、ＨＣＦＣ、及びＣＦＣに対する代替物もまた探し求められている。 Chlorofluorocarbons (CFCs) such as trichlorofluoromethane and dichlorodifluoromethane are traditionally used as refrigerants, blowing agents, and diluents for gas sterilization. In recent years, there is a general concern that all halogenated chlorofluorocarbons can be harmful to the Earth's ozone layer. Therefore, alternatives to these materials that are safer for the stratosphere are desired. Currently, there is a worldwide effort to use fluorine substituted hydrocarbons that contain little or no chlorine substituents. The manufacture of HFCs, ie compounds containing only carbon, hydrogen, and fluorine, is an interesting subject to provide environmentally desirable products that provide an alternative to CFCs. It is known in the art to produce such compounds by reacting hydrogen fluoride with various hydrochlorocarbon compounds. HFC is considered to be much more environmentally advantageous than hydrochlorofluorocarbon (HCFC) or chlorofluorocarbon (CFC) because it is not non-ozone depleting, but recent data It indicates that the greenhouse effect may contribute to global warming. Therefore, alternatives to HFC, HCFC, and CFC are also sought.
ヒドロフルオロオレフィン（ＨＦＯ）が可能な代替物として提案されている。ＨＦＯは単一成分の流体又は共沸性混合物として最も良好に用いられることが一般に知られているが、これらのいずれも沸騰及び蒸発によっては分別されない。かかる組成物の確認は、少なくとも部分的に共沸混合物の形成の相対的な予測不能性のために困難である。したがって、産業界は、ＣＦＣ、ＨＣＦＣ、及びＨＦＣに関する許容でき且つ環境により優しい代替物である新規なＨＦＯベースの混合物を継続的に探し求めている。本発明はとりわけこれらの必要性を満足する。 Hydrofluoroolefin (HFO) has been proposed as a possible alternative. Although it is generally known that HFO is best used as a single component fluid or azeotropic mixture, none of these are fractionated by boiling and evaporation. Confirmation of such compositions is difficult due at least in part to the relative unpredictability of azeotrope formation. Therefore, the industry is continually seeking new HFO-based mixtures that are acceptable and environmentally friendly alternatives for CFCs, HCFCs, and HFCs. The present invention satisfies these needs among others.
本発明は、トランス−１，１，１，４，４，４−ヘキサフルオロ−２−ブテン（ＨＦＯ−１３３６ｍｚｚ（Ｅ））及び水の共沸性又は共沸混合物様の組成物を提供する。ＨＦＯ−１３３６ｍｚｚ（Ｅ）及び水は低いか又はゼロのオゾン層破壊係数を有しているので、本発明の組成物は現在用いられているＣＦＣ、ＨＦＣ、及びＨＣＦＣに関する環境的に望ましい代替物を提供する。更に、かかる共沸混合物を含む組成物は、それをＣＦＣ、ＨＦＣ、及びＨＣＦＣ代替物、並びにＨＦＯ−１３３６ｍｚｚ（Ｅ）又は水単独よりも良好にする特性を示す。 The present invention provides an azeotropic or azeotrope-like composition of trans-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz (E)) and water. Because HFO-1336mzz (E) and water have a low or zero ozone depletion potential, the compositions of the present invention represent an environmentally desirable alternative to currently used CFCs, HFCs, and HCFCs. provide. Furthermore, compositions containing such azeotropes exhibit properties that make them better than CFC, HFC, and HCFC substitutes, and HFO-1336mzz (E) or water alone.
本発明は更に、０より多く約５０重量％までの水、及び約５０乃至約１００重量％未満のＨＦＯ−１３３６ｍｚｚ（Ｅ）のブレンドを含み、得られる共沸混合物は約１４．５ｐｓｉａ±２ｐｓｉａの圧力において約７．０℃±１℃の沸点を有する組成物及び共沸性又は共沸混合物様の組成物を形成する方法を提供する。更なる態様においては、共沸混合物は約１４．５ｐｓｉａの圧力において約７℃の沸点を有し、更なる態様においては、共沸混合物は約１４．５ｐｓｉａの圧力において約７．０℃の沸点を有する。 The present invention further comprises a blend of greater than 0 to about 50 wt.% Water and from about 50 to less than about 100 wt.% HFO-1336mzz (E), the resulting azeotrope being about 14.5 psia ± 2 psia. Compositions having boiling points of about 7.0 ° C. ± 1 ° C. at pressure and methods for forming azeotropic or azeotrope-like compositions are provided. In a further embodiment, the azeotrope has a boiling point of about 7 ° C. at a pressure of about 14.5 psia, and in a further embodiment, the azeotrope has a boiling point of about 7.0 ° C. at a pressure of about 14.5 psia. Have
本発明はまた、上記の重量％にしたがう共沸性又は共沸混合物様の組成物を形成するのに十分な量の水を混合物に加えることによって、ＨＦＯ−１３３６ｍｚｚ（Ｅ）及び少なくとも１種類の不純物を含む混合物からＨＦＯ−１３３６ｍｚｚ（Ｅ）を取り出す方法にも関する。次に、蒸留など（しかしながらこれに限定されない）の当該技術において公知の標準的な方法を用いて、この共沸混合物を不純物から分離する。不純物としてはハロカーボン又はフッ化水素を挙げることができ、これらはＨＦＯ−１３３６ｍｚｚ（Ｅ）と混和性であってもなくてもよい。ハロカーボンの例としては、１−クロロ−３，３，３−トリフルオロプロペン及びシス−１，１，１，４，４，４−ヘキサフルオロ−２−ブテンが挙げられるが、これらに限定されない。更なる態様においては、不純物は、ＨＦＯ−１３３６ｍｚｚ（Ｅ）、水、又はＨＦＯ−１３３６ｍｚｚ（Ｅ）と水との混合物と共沸性の混合物を形成しても又はしなくてもよい。 The present invention also provides for adding HFO-1336mzz (E) and at least one type of water to the mixture by adding a sufficient amount of water to form an azeotropic or azeotrope-like composition according to the above weight percent. The present invention also relates to a method for extracting HFO-1336mzz (E) from a mixture containing impurities. The azeotrope is then separated from the impurities using standard methods known in the art, such as but not limited to distillation. Impurities can include halocarbons or hydrogen fluoride, which may or may not be miscible with HFO-1336mzz (E). Examples of halocarbons include, but are not limited to, 1-chloro-3,3,3-trifluoropropene and cis-1,1,1,4,4,4-hexafluoro-2-butene. . In further embodiments, the impurities may or may not form an azeotropic mixture with HFO-1336mzz (E), water, or a mixture of HFO-1336mzz (E) and water.
本発明はまた、ＨＦＯ−１３３６ｍｚｚ（Ｅ）を水から分離することによって、ＨＦＯ−１３３６ｍｚｚ（Ｅ）及び水の共沸性混合物からのＨＦＯ−１３３６ｍｚｚ（Ｅ）に関する方法にも関する。分離法としては、当該技術において公知か又は本明細書において他に議論する方法の任意の１つ又は組み合わせを挙げることができる。例えば、液−液相分離を用いてＨＦＯ−１３３６ｍｚｚ（Ｅ）を分離することができる。別の態様においては、乾燥媒体（例えば、モレキュラーシーブ、シリカアルミナなど）を用いてＨＦＯ−１３３６ｍｚｚ（Ｅ）を分離することができる。本発明の更なる態様及び有利性は、本明細書に与える開示事項に基づいて当業者に明らかになるであろう。 The invention also relates to a process for HFO-1336mzz (E) and HFO-1336mzz (E) from an azeotropic mixture of water by separating HFO-1336mzz (E) from water. Separation methods can include any one or combination of methods known in the art or discussed elsewhere herein. For example, HFO-1336mzz (E) can be separated using liquid-liquid phase separation. In another embodiment, a drying medium (eg, molecular sieve, silica alumina, etc.) can be used to separate HFO-1336mzz (E). Further aspects and advantages of the present invention will become apparent to those skilled in the art based on the disclosure provided herein.
本発明の第１の形態においては、ＨＦＯ−１３３６ｍｚｚ（Ｅ）及び水の共沸性又は共沸混合物様の組成物が提供される。ＨＦＯ−１３３６ｍｚｚ（Ｅ）及び水は低いか又はゼロのオゾン層破壊係数を有しているので、この組成物は現在用いられているＣＦＣ、ＨＦＣ、及びＨＣＦＣに関する環境的に望ましい代替物を提供する。更に、かかる共沸混合物を含む組成物は、それをＣＦＣ、ＨＦＣ、及びＨＣＦＣ代替物、並びにＨＦＯ−１３３６ｍｚｚ（Ｅ）又は水単独よりも良好にする特性を示す。本発明の第２の形態においては、ＨＦＯ−１３３６ｍｚｚ（Ｅ）及び水の共沸混合物又は共沸混合物様の組成物を用いて、純粋形態のＨＦＯ−１３３６ｍｚｚ（Ｅ）を単離する。 In a first aspect of the invention, an azeotropic or azeotrope-like composition of HFO-1336mzz (E) and water is provided. Since HFO-1336mzz (E) and water have a low or zero ozone depletion potential, this composition provides an environmentally desirable alternative for currently used CFCs, HFCs, and HCFCs . Furthermore, compositions containing such azeotropes exhibit properties that make them better than CFC, HFC, and HCFC substitutes, and HFO-1336mzz (E) or water alone. In a second form of the invention, HFO-1336mzz (E) and water azeotrope or azeotrope-like composition is used to isolate pure form of HFO-1336mzz (E).
本発明の目的のためには、ＨＦＯ−１３３６ｍｚｚ（Ｅ）及び水の共沸混合物又は共沸混合物様の混合物は、共沸混合物のように挙動するこれらの組成物又は混合物を含む。流体の熱力学的状態は、その圧力、温度、液体組成、及び蒸気組成によって規定される。真の共沸性組成物に関しては、規定された温度及び圧力範囲において液体組成と蒸気相が実質的に等しい。実際面では、これは成分を相変化中に分離することができないことを意味する。本発明の目的のためには、共沸混合物は、周囲混合物組成物の沸点と比べて最高又は最低の沸点を示す液体混合物である。共沸混合物又は共沸混合物様の組成物は、与えられた圧力下において液体形態である場合に実質的に一定の温度において沸騰し、その温度が成分の沸点よりも高いか又は低い可能性があり、沸騰している液体組成物と実質的に同一の蒸気組成を与える２以上の異なる成分の混合物である。本発明の目的のためには、共沸性組成物は、共沸混合物様の組成物（これは、共沸混合物のように挙動し、即ち一定の沸点特性を有するか、或いは沸騰又は蒸発させることによって分別されない傾向を有する組成物を意味する）を包含するように定義される。而して、沸騰又は蒸発中に形成される蒸気の組成は、元の液体の組成と同じか又は実質的に同じである。したがって、沸騰又は蒸発中において、液体の組成は、変化するとしても、最小又は無視できる程度までしか変化しない。これは、沸騰又は蒸発中に液体の組成が相当程度まで変化する非共沸混合物様の組成物とは対照的である。したがって、共沸混合物又は共沸混合物様の組成物の重要な特徴は、与えられた圧力において、液体組成物の沸点が一定であり、沸騰している組成物の上方の蒸気の組成が、実質的に、沸騰している液体組成物のものであり、即ち、液体組成物の成分の分別が実質的に起こらないことである。共沸性組成物のそれぞれの成分の沸点及び重量％は両方とも、共沸混合物又は共沸混合物様の液体組成物を異なる圧力において沸騰にかけると変化する可能性がある。而して、共沸混合物又は共沸混合物様の組成物は、その成分間に存在する関係の観点、又は成分の組成範囲の観点、又は規定圧力における一定の沸点によって特徴付けられる組成物のそれぞれの成分の実際の重量％の観点で規定することができる。 For the purposes of the present invention, an azeotrope or azeotrope-like mixture of HFO-1336mzz (E) and water includes those compositions or mixtures that behave like an azeotrope. The thermodynamic state of a fluid is defined by its pressure, temperature, liquid composition, and vapor composition. For true azeotropic compositions, the liquid composition and the vapor phase are substantially equal over the specified temperature and pressure ranges. In practice, this means that the components cannot be separated during the phase change. For the purposes of the present invention, an azeotrope is a liquid mixture that exhibits the highest or lowest boiling point relative to the boiling point of the surrounding mixture composition. An azeotrope or azeotrope-like composition will boil at a substantially constant temperature when in liquid form under a given pressure, and the temperature may be higher or lower than the boiling point of the components. A mixture of two or more different components that provides a vapor composition that is substantially identical to the boiling liquid composition. For the purposes of the present invention, an azeotropic composition is an azeotrope-like composition (which behaves like an azeotrope, ie has a certain boiling characteristic or is boiled or evaporated. Meaning a composition having a tendency not to be separated). Thus, the composition of the vapor formed during boiling or evaporation is the same or substantially the same as the composition of the original liquid. Thus, during boiling or evaporation, the composition of the liquid, if any, changes only to a minimum or negligible level. This is in contrast to non-azeotrope-like compositions where the composition of the liquid changes to a significant extent during boiling or evaporation. Thus, an important feature of an azeotrope or azeotrope-like composition is that, at a given pressure, the boiling point of the liquid composition is constant and the composition of the vapor above the boiling composition is substantially In particular, it is of a boiling liquid composition, i.e., the fractionation of the components of the liquid composition does not occur substantially. Both the boiling point and weight percent of each component of the azeotropic composition can change when the azeotrope or azeotrope-like liquid composition is boiled at different pressures. Thus, an azeotrope or azeotrope-like composition is a composition characterized by a relationship existing between its components, or by a composition range of components, or by a constant boiling point at a specified pressure, respectively. In terms of the actual weight percent of the components.
したがって、本発明は有効量のＨＦＯ−１３３６ｍｚｚ（Ｅ）及び水の共沸混合物様の組成物を提供する。本明細書において用いる「有効量」とは、他の成分と組み合わせることによって共沸混合物様の組成物を形成するそれぞれの成分の量を意味する。より具体的には、共沸性混合物は、共沸性又は共沸混合物様の組成物の重量を基準として約０より多く約５０％までの水、及び約５０乃至約１００％未満のＨＦＯ−１３３６ｍｚｚ（Ｅ）を含む。本発明の共沸性混合物は、約１４．５±２ｐｓｉａの圧力において約７．０℃±１℃の沸点を有する。更なる態様においては、本発明の共沸性混合物は、約１４．５の圧力において約７℃の沸点を有する。更なる態様においては、共沸混合物は約１４．５ｐｓｉａの圧力において約７．０℃の沸点を有する。 Thus, the present invention provides an azeotrope-like composition of effective amounts of HFO-1336mzz (E) and water. As used herein, “effective amount” means the amount of each component that, when combined with other components, forms an azeotrope-like composition. More specifically, the azeotropic mixture is from about 0 to about 50% water, and from about 50 to less than about 100% HFO-, based on the weight of the azeotropic or azeotrope-like composition. 1336mzz (E) is included. The azeotropic mixture of the present invention has a boiling point of about 7.0 ° C. ± 1 ° C. at a pressure of about 14.5 ± 2 psia. In a further embodiment, the azeotropic mixture of the present invention has a boiling point of about 7 ° C. at a pressure of about 14.5. In a further embodiment, the azeotrope has a boiling point of about 7.0 ° C. at a pressure of about 14.5 psia.
第１の態様においては、本発明の方法は、ＨＦＯ−１３３６ｍｚｚ（Ｅ）及びＨＦＯ−１３３６ｍｚｚ（Ｅ）／水の共沸混合物を生成させ、共沸混合物を不純物から単離する工程を含む。本発明はまた、下記により詳細に議論する、共沸性混合物からＨＦＯ−１３３６ｍｚｚ（Ｅ）を精製する工程も含む。この精製した共沸混合物は、オゾン層破壊係数を有さず、温室効果地球温暖化に無視できる程度しか寄与せず、不燃性であるというＨＦＯ混合物に対する当該技術における必要性を満足する。かかる混合物は、冷媒、発泡剤、噴射剤、及びガス滅菌用の希釈剤など（しかしながらこれらに限定されない）の広範囲の用途において用いることができる。この共沸混合物は、かかる目的のための他の有用な添加剤又は成分と組み合わせて与えることができる。 In a first aspect, the method of the present invention comprises the steps of forming an azeotrope of HFO-1336mzz (E) and HFO-1336mzz (E) / water and isolating the azeotrope from impurities. The present invention also includes purifying HFO-1336mzz (E) from an azeotropic mixture, discussed in more detail below. This refined azeotrope does not have an ozone depletion potential, contributes negligibly to greenhouse global warming, and satisfies the need in the art for HFO mixtures to be non-flammable. Such mixtures can be used in a wide range of applications such as, but not limited to, refrigerants, blowing agents, propellants, and diluents for gas sterilization. This azeotrope can be provided in combination with other useful additives or ingredients for such purposes.
第２の態様においては、ＨＦＯ−１３３６ｍｚｚ（Ｅ）及び水の共沸混合物の成分部分を精製形態のＨＦＯ−１３３６ｍｚｚ（Ｅ）に分離することも望ましい可能性がある。分離法としては、当該技術において一般的に知られている任意の方法を挙げることができる。例えば一態様においては、液−液相分離によってＨＦＯ−１３３６ｍｚｚ（Ｅ）から過剰の水を除去することができる。次に、蒸留及び／又は乾燥媒体（例えば、モレキュラーシーブ、シリカアルミナなど）によって残りの水をＨＦＯ−１３３６ｍｚｚ（Ｅ）から除去することができる。精製したＨＦＯ−１３３６ｍｚｚ（Ｅ）は、最終生成物として（即ち、冷媒、発泡剤、噴射剤、気体滅菌用の希釈剤などとして）用いることができ、或いは別のＨＦＯ又は同様の化合物を製造するために更に処理することができる。以下の非限定的な実施例は本発明を例示するように働く。 In the second aspect, it may also be desirable to separate the component parts of the azeotrope of HFO-1336mzz (E) and water into purified forms of HFO-1336mzz (E). Examples of the separation method include any method generally known in the art. For example, in one embodiment, excess water can be removed from HFO-1336mzz (E) by liquid-liquid phase separation. The remaining water can then be removed from HFO-1336mzz (E) by distillation and / or drying media (eg, molecular sieves, silica alumina, etc.). Purified HFO-1336mzz (E) can be used as a final product (ie, as a refrigerant, blowing agent, propellant, diluent for gas sterilization, etc.) or produces another HFO or similar compound Can be further processed. The following non-limiting examples serve to illustrate the invention.
実施例１：
ドライアイス冷却凝縮器を取り付けたガラス製の真空断熱容器に、まずＨＦＯ−１３３６ｍｚｚ（Ｅ）を充填した。次に水を徐々に加えて、混合物の温度を記録した。混合物の温度は最低値に達し、次に平坦になり、これは不均一共沸混合物が形成されたことを示す。測定中の雰囲気圧力は１４．５ｐｓｉａであった。測定された温度を表１に示す。
Example 1:
First, HFO-1336mzz (E) was charged into a glass vacuum insulated container fitted with a dry ice cooling condenser. Then water was added slowly and the temperature of the mixture was recorded. The temperature of the mixture reached the lowest value and then flattened, indicating that a heterogeneous azeotrope was formed. The atmospheric pressure during the measurement was 14.5 psia. Table 1 shows the measured temperatures.
［１］
有効量のトランス-１，１，１，４，４，４−ヘキサフルオロ−２−ブテン（ＨＦＯ−１３３６ｍｚｚ（Ｅ））及び水から実質的に構成される共沸性又は共沸混合物様の組成物。
［２］
約０より多く約５０重量％までの水、及び約５０乃至約１００重量％未満のＨＦＯ−１３３６ｍｚｚ（Ｅ）から実質的に構成され、約１４．５ｐｓｉａ±２ｐｓｉａの圧力において約７．０℃±１℃の沸点を有する共沸性又は共沸混合物様の組成物。
［３］
水及びＨＦＯ−１３３６ｍｚｚ（Ｅ）から構成される、［２］に記載の組成物。
［４］
約１４．５ｐｓｉａの圧力において約７．０℃の沸点を有する、［２］に記載の組成物。
［５］
約０〜約５０重量％の水、及び約５０乃至約１００重量％未満のＨＦＯ−１３３６ｍｚｚ（Ｅ）から実質的に構成されるブレンドを形成することを含む、約１４．５ｐｓｉａ±２ｐｓｉａの圧力において約７．０℃±１℃の沸点を有する共沸性又は共沸混合物様の組成物を形成する方法。
［６］
組成物が水及びＨＦＯ−１３３６ｍｚｚ（Ｅ）から構成される、［５］に記載の方法。
［７］
ＨＦＯ−１３３６ｍｚｚ（Ｅ）及び少なくとも１種類の不純物の混合物からＨＦＯ−１３３６ｍｚｚ（Ｅ）を取り出す方法であって、ＨＦＯ−１３３６ｍｚｚ（Ｅ）及び水の共沸性又は共沸混合物様の組成物を形成するのに十分な量の水を混合物に加え、そして不純物から共沸性組成物を分離することを含む上記方法。
［８］
不純物が、ＨＦＯ−１３３６ｍｚｚ（Ｅ）、水、又はＨＦＯ−１３３６ｍｚｚ（Ｅ）と水との混合物と共沸性混合物を形成しない、［７］に記載の方法。
［９］
不純物が、ＨＦＯ−１３３６ｍｚｚ（Ｅ）、水、又はＨＦＯ−１３３６ｍｚｚ（Ｅ）と水との混合物と共沸性混合物を形成する、［７］に記載の方法。
［１０］
不純物がハロカーボンを含む、［７］に記載の方法。
[1]
An azeotropic or azeotrope-like composition consisting essentially of an effective amount of trans-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz (E)) and water. object.
[2]
Substantially composed of greater than about 0 up to about 50% by weight water, and from about 50 to less than about 100% by weight HFO-1336mzz (E), and at a pressure of about 14.5 psia ± 2 psia at about 7.0 ° C. ± An azeotropic or azeotrope-like composition having a boiling point of 1 ° C.
[3]
The composition according to [2], which is composed of water and HFO-1336mzz (E).
[4]
The composition of [2], having a boiling point of about 7.0 ° C. at a pressure of about 14.5 psia.
[5]
At a pressure of about 14.5 psia ± 2 psia, comprising forming a blend substantially composed of about 0 to about 50 wt% water, and about 50 to less than about 100 wt% HFO-1336mzz (E). A method of forming an azeotropic or azeotrope-like composition having a boiling point of about 7.0 ° C. ± 1 ° C.
[6]
The method according to [5], wherein the composition is composed of water and HFO-1336mzz (E).
[7]
A method for removing HFO-1336mzz (E) from a mixture of HFO-1336mzz (E) and at least one impurity, forming an azeotropic or azeotrope-like composition of HFO-1336mzz (E) and water Adding a sufficient amount of water to the mixture and separating the azeotropic composition from impurities.
[8]
The method according to [7], wherein the impurities do not form an azeotropic mixture with HFO-1336mzz (E), water, or a mixture of HFO-1336mzz (E) and water.
[9]
The method of [7], wherein the impurities form an azeotropic mixture with HFO-1336mzz (E), water, or a mixture of HFO-1336mzz (E) and water.
[10]
The method according to [7], wherein the impurity comprises a halocarbon.
Claims (3)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US13/009,198 | 2011-01-19 | ||
| US13/009,198 US8066901B1 (en) | 2011-01-19 | 2011-01-19 | Azeotrope-like compositions of trans-1,1,1,4,4,4-hexafluoro-2-butene and water |
| PCT/US2012/021494 WO2012099844A2 (en) | 2011-01-19 | 2012-01-17 | Azeotrope-like compositions of trans-1,1,1,4,4,4-hexafluoro-2-butene and water |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2014503033A JP2014503033A (en) | 2014-02-06 |
| JP5970000B2 true JP5970000B2 (en) | 2016-08-17 |
Family
ID=44994319
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2013550529A Active JP5970000B2 (en) | 2011-01-19 | 2012-01-17 | An azeotrope-like composition of trans-1,1,1,4,4,4-hexafluoro-2-butene and water |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US8066901B1 (en) |
| EP (2) | EP2665793B1 (en) |
| JP (1) | JP5970000B2 (en) |
| CN (1) | CN103370390B (en) |
| DK (1) | DK2665793T3 (en) |
| ES (1) | ES2641620T3 (en) |
| MX (1) | MX352524B (en) |
| NO (1) | NO2665793T3 (en) |
| PL (1) | PL2665793T3 (en) |
| PT (1) | PT2665793T (en) |
| WO (1) | WO2012099844A2 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8454853B2 (en) * | 2008-03-07 | 2013-06-04 | Arkema Inc. | Halogenated alkene heat transfer composition with improved oil return |
| AU2010295687B2 (en) * | 2009-09-16 | 2014-11-06 | E. I. Du Pont De Nemours And Company | Chiller apparatus containing trans-1,1,1,4,4,4-hexafluoro-2-butene and methods of producing cooling therein |
| US8846754B2 (en) | 2009-12-16 | 2014-09-30 | Honeywell International Inc. | Azeotrope-like compositions of cis-1,1,1,4,4,4-hexafluoro-2-butene |
| US8066901B1 (en) | 2011-01-19 | 2011-11-29 | Honeywell International Inc. | Azeotrope-like compositions of trans-1,1,1,4,4,4-hexafluoro-2-butene and water |
| CN109280541B (en) * | 2017-07-19 | 2021-02-12 | 浙江省化工研究院有限公司 | Environment-friendly composition |
| CN108359121B (en) | 2017-12-14 | 2019-03-15 | 浙江衢化氟化学有限公司 | A kind of azeotropic and Azeotrope-like compositions |
| WO2020150437A1 (en) * | 2019-01-17 | 2020-07-23 | The Chemours Company Fc, Llc | Azeotrope and azeotrope-like compositions comprising (e)-1,1,1,4,4,4-hexafluorobut-2-ene |
| CN112795372B (en) * | 2021-04-08 | 2021-07-16 | 泉州宇极新材料科技有限公司 | Azeotropic or azeotrope-like compositions comprising chain-like and cyclic fluorides |
| CN113789155B (en) * | 2021-09-16 | 2022-06-28 | 珠海格力电器股份有限公司 | Mixed refrigerant and air conditioning system |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05179043A (en) | 1991-11-18 | 1993-07-20 | Daikin Ind Ltd | Blowing agent comprising fluorobutene and production of plastic foam |
| EP0670295B1 (en) * | 1992-11-20 | 1998-07-29 | Daikin Industries, Limited | Process for producing 1,1,1,4,4,4-hexafluoro-2-butene and 1,1,1,4,4,4,-hexafluorobutane |
| US7897823B2 (en) | 2004-10-29 | 2011-03-01 | E. I. Du Pont De Nemours And Company | Process for production of azeotrope compositions comprising hydrofluoroolefin and hydrogen fluoride and uses of said azeotrope compositions in separation processes |
| CA2626183C (en) | 2005-11-01 | 2016-11-29 | E. I. Du Pont De Nemours And Company | Compositions comprising fluoroolefins and uses thereof |
| US7803975B2 (en) | 2006-07-13 | 2010-09-28 | E.I. Du Pont De Nemours And Company | Process for separating a fluoroolefin from HF by liquid-liquid extraction |
| JP5592249B2 (en) | 2007-03-27 | 2014-09-17 | ダウ グローバル テクノロジーズ エルエルシー | High quality polymer foam from fluorinated alkene blowing agent |
| EP2139568B8 (en) | 2007-04-27 | 2018-04-25 | The Chemours Company FC, LLC | Azeotropic composition of z-1,1,1,4,4,4-hexafluoro-2-butene and methyl formate |
| AU2008261695B2 (en) * | 2007-06-12 | 2013-05-30 | The Chemours Company Fc, Llc. | Azeotropic and azeotrope-like compositions of E-1,1,1,4,4,4-hexafluoro-2-butene |
| US20090204443A1 (en) * | 2008-02-08 | 2009-08-13 | Honeywell International Inc. | Integrated roof wind risk mitigation method and system |
| MX2010014094A (en) | 2008-06-20 | 2011-01-21 | Du Pont | Azeotropic and azeotrope-like compositions of z-1,1,1,4,4,4-hexafluoro-2-butene. |
| US8609909B2 (en) * | 2009-01-30 | 2013-12-17 | Honeywell International Inc. | Process for the purification of hydrofluoroolefins |
| US8846754B2 (en) * | 2009-12-16 | 2014-09-30 | Honeywell International Inc. | Azeotrope-like compositions of cis-1,1,1,4,4,4-hexafluoro-2-butene |
| US8066901B1 (en) | 2011-01-19 | 2011-11-29 | Honeywell International Inc. | Azeotrope-like compositions of trans-1,1,1,4,4,4-hexafluoro-2-butene and water |
-
2011
- 2011-01-19 US US13/009,198 patent/US8066901B1/en active Active
-
2012
- 2012-01-17 WO PCT/US2012/021494 patent/WO2012099844A2/en active Application Filing
- 2012-01-17 PT PT127364248T patent/PT2665793T/en unknown
- 2012-01-17 JP JP2013550529A patent/JP5970000B2/en active Active
- 2012-01-17 EP EP12736424.8A patent/EP2665793B1/en active Active
- 2012-01-17 DK DK12736424.8T patent/DK2665793T3/en active
- 2012-01-17 EP EP17186308.7A patent/EP3305751A1/en active Pending
- 2012-01-17 CN CN201280005839.3A patent/CN103370390B/en active Active
- 2012-01-17 MX MX2013008203A patent/MX352524B/en active IP Right Grant
- 2012-01-17 NO NO12736424A patent/NO2665793T3/no unknown
- 2012-01-17 PL PL12736424T patent/PL2665793T3/en unknown
- 2012-01-17 ES ES12736424.8T patent/ES2641620T3/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| EP2665793A4 (en) | 2015-12-23 |
| PT2665793T (en) | 2017-10-03 |
| ES2641620T3 (en) | 2017-11-10 |
| EP3305751A1 (en) | 2018-04-11 |
| MX2013008203A (en) | 2013-09-26 |
| MX352524B (en) | 2017-11-29 |
| WO2012099844A2 (en) | 2012-07-26 |
| US8066901B1 (en) | 2011-11-29 |
| JP2014503033A (en) | 2014-02-06 |
| WO2012099844A3 (en) | 2012-10-18 |
| EP2665793B1 (en) | 2017-08-16 |
| NO2665793T3 (en) | 2018-01-13 |
| PL2665793T3 (en) | 2018-01-31 |
| DK2665793T3 (en) | 2017-11-27 |
| CN103370390B (en) | 2016-01-20 |
| CN103370390A (en) | 2013-10-23 |
| EP2665793A2 (en) | 2013-11-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5934699B2 (en) | An azeotrope-like composition of tetrafluoropropene and water | |
| JP5970000B2 (en) | An azeotrope-like composition of trans-1,1,1,4,4,4-hexafluoro-2-butene and water | |
| USRE46928E1 (en) | Azeotrope-like compositions of pentafluoropropene and water | |
| JP5961182B2 (en) | (Z) An azeotrope-like composition of 1-chloro-3,3,3-trifluoropropene and hydrogen fluoride | |
| JP2016222924A (en) | Azeotrope-like composition of hexafluoropropane, hexafluoropropene and hydrogen fluoride | |
| KR102630950B1 (en) | Azeotropic or azeotrope-like compositions of 3,3,3-trifluoropropyne and water |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20130919 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20150109 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20160129 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20160205 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20160422 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20160609 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20160708 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5970000 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |